Haloacyl and thiohaloacyl aryl-substituted oxazolidines and thiazolidines-herbicidal antidotes

ABSTRACT

Haloacyl and thiohaloacyl aryl-substituted oxazolidines and thiazolidines useful as active antidotes against crop injury when used with various herbicides; herbicidal compositions and utility of various herbicides and aryl substituted oxazolidines and thiazolidines having the formula ##STR1## wherein X and Y are independently oxygen or sulfur; R is haloalkyl or chloroalkenyl; R 1  is hydrogen, lower alkyl, phenyl, naphthyl, substituted phenyl wherein said substituents are monofluoro, mono- or di- chloro, nitro, methyl, methoxy, or hydroxyl; R 2  is hydrogen or lower alkyl; R 3  is hydrogen, lower alkyl, hydroxymethyl, N-methyl carbamoyloxymethyl or dichloroacetoxymethyl; R 4  is hydrogen or lower alkyl; R 5  is hydrogen, lower alkyl or phenyl; and R 6  is hydrogen; provided that at least one of R 1  or R 5  is phenyl, substituted phenyl or naphthyl.

CROSS-REFERENCE TO PRIOR APPLICATION

This application is a continuation-in-part of copending application Ser. No. 550,069, filed Feb. 14, 1975, now abandoned.

BACKGROUND OF THE INVENTION

While many herbicides are immediately toxic to a large number of weed pests, it is known that the effect of many herbicides upon important plant cultivations is either non-selective or not adequately selective. Thus, many herbicides damage not only the weeds to be controlled but, to a greater or lesser extent, the desirable cultivated plants as well. This holds true for many herbicidal compounds which have been commercially successful and are commercially available. These herbicides include types such as triazines, urea derivatives, halogenated acetanilides, carbamates, thiocarbamates and the like. Some examples of these compounds are described in U.S. Pat. Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and 3,582,314.

The side effect of injury to a cultivated crop by various herbicides is particularly inconvenient and unfortunate. When used in the recommended amounts in the soil to control broadleaf weeds and grasses, serious malformation or stunting of the crop plants sometimes result. This abnormal growth in the crop plants results in loss of crop yield. The search continues for good selective herbicides.

Previous attempts are described to overcome this problem. The treatment of the crop seed with certain "hormonal" antagonistic agents prior to planting is described; see U.S. Pat. Nos. 3,131,509 and 3,564,768. The protective agents, as well as the herbicide, in these prior processes are largely specific to certain cultivated plant species. The antagonistic agents have not been notably successful. The aforementioned patents specifically exemplify and describe the treatment of seeds employing compounds of a different chemical class, not suggestive of the present invention.

DESCRIPTION OF THE INVENTION

It has been discovered that cultivated crop plants can be protected against injury by thiocarbamate-type herbicides and by halogenated acetanilide herbicides, each alone or in mixtures or combination with other compounds. Further, as an alternative effect, the tolerance of the plants to these herbicides can be substantially increased by adding to the soil an antidote compound corresponding to the following formula ##STR2## wherein X and Y are independently oxygen or sulfur; R is haloalkyl or chloro alkenyl; R₁ is hydrogen, lower alkyl, phenyl, naphthyl, substituted phenyl wherein said substituents are monofluoro, mono- or di- chloro, nitro, methyl, methoxy or hydroxyl; R₂ is hydrogen or lower alkyl; R₄ is hydrogen or lower alkyl; R₃ is hydrogen, lower alkyl, hydroxymethyl, N-methyl carbamoyloxymethyl or dichloroacetoxymethyl; R₅ is hydrogen, lower alkyl or phenyl; and R₆ is hydrogen; provided that at least one of R₁ or R₅ is phenyl, substituted phenyl or naphthyl.

Certain of the compounds disclosed herein are considered new compositions and correspond to the following formula ##STR3## in which X and Y are independently oxygen or sulfur; R is haloalkyl or chloroalkenyl; R₁ is hydrogen, lower alkyl or phenyl; R₂ is hydrogen or lower alkyl; R₃ is hydrogen or lower alkyl; R₄ is hydrogen or lower alkyl; R₅ is phenyl and R₆ is hydrogen.

In the above description, the following embodiments are intended for the various substituent groups: For R, haloalkyl preferably includes those members which contain from 1 to 6 carbon atoms, inclusive, in both straight chain and branched chain configurations and the term halo includes chloro and bromo as mono, di, tri and tetra substitutions. As exemplary of the alkyl portion within the preferred embodiment are the following: Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, 1,1-dimethylbutyl, amyl, isoamyl, n-hexyl and isohexyl. For R, chloro alkenyl preferably includes those members which contain from 2 to 4 carbon atoms and at least one olefinic double bond and the chloro substituents are present as mono-, di-, tri-, or tetra- substitutions, such as trichlorovinyl. For R₁, R₂, R₃, R₄ and R₅, lower alkyl in each instance preferably includes those members which contain from 1 to 4 carbon atoms, inclusive, in both straight chain and branched chain configurations, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl tert.-butyl and the like.

As an alternative mode of action, the compounds of this invention may interfere with the normal herbicidal action of the thiocarbamate-type and other herbicides to render them selective in their action. Whichever mode of action is present, the corresponding beneficial and desirable effect is the continued herbicidal effect of the thiocarbamate with the accompanying decreased herbicidal effect on desired crop species. This advantage and utility will become more apparent hereinafter.

Therefore, the terms herbicide antidote or antidotal amount, is meant to describe that effect which tends to counteract the normal injurious herbicidal response that the herbicide might otherwise produce. Whether it is to be termed a remedy, interferant, protectant, or the like, will depend upon the exact mode of action. The mode of action is varied, but the effect, which is desirable, is the result of the method of treating the soil in which a crop is planted. Hitherto, there have been no systems which have been satisfactory for this purpose.

The compounds of this invention represented by the above formula can be prepared by several different procedures depending upon the starting materials.

The oxazolidine and thiazolidine intermediates were prepared by the condensation of the amino alcohol or mercaptan with a suitable aldehyde or ketone in boiling benzene with the continuous separation of water. This method is described by Bergmann et al., JACS 75 358 (1953). Usually, the oxazolidines and thiazolidines intermediates were pure enough to be used directly without further purification. Aliquots of these solutions were then used to prepare the compounds of this invention.

Compounds having a 3- thioacylsubstitution may be prepared from the corresponding oxygen analogues by methods known in the synthetic organic literature, such as treatment with P₂ S₅

The appropriate intermediate was reacted with an acid chloride in the presence of a hydrogen chloride acceptor, such as triethylamine, to prepare the desired compound. Work-up and purification procedures involved standard methods of extraction, distillation or crystallization.

The compounds of the present invention and their preparation are more particularly illustrated by the following examples. Following the examples of preparation is a table of compounds which are prepared according to the procedures described herein. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

EXAMPLE I Preparation of 2-m-nitrophenyl-3-dichloroacetyl oxazolidine.

Five and eight tenths grams of 2-m-nitrophenyl oxazolidine was dissolved in 50 ml. methylene chloride containing 3.5 g. of triethylamine. Dichloroacetyl chloride 4.4 g. was added dropwise with stirring to the reaction flask and cooled in a water bath at room temperature. When addition was complete, the mixture was stirred at room temperature for about 30 minutes, washed with water, separated and dried over anhydrous magnesium sulfate. The solvent was stripped off under vacuum. There was obtained a yield of 8.6 g. of the title compound, N_(D) ³⁰ = 1.5590.

EXAMPLE II Preparation of 2-ethyl-3-dichloroacetyl-5-phenyl oxazolidine.

Twenty-one and three tenths ml. of a solution containing 5.3 g of 2-ethyl-5-phenyl oxazolidine was diluted with 25 ml. of benzene and 3.1 g. of triethylamine was added. The mixture was cooled in a room temperature water bath and 4.4 g. of dichloroacetyl chloride was added dropwise with stirring. The stirring was continued for about 30 minutes after addition was complete. The solution was washed with water, separated, dried over magnesium sulfate and removed under vacuum. There was obtained a yield of 8.7 g. of the title compound, an oil, N_(D) ³⁰ = 1.5600.

EXAMPLE III Preparation of 2,2-dimethyl-3-dichloroacetyl-5-phenyl oxazolidine.

One hundred grams of 1-phenyl-2-amino ethanol was dissolved in 250 ml. of benzene and 45 g. of acetone was added. The mixture was heated at reflux for several hours while about 15 ml. of water was removed with a modified Dean-Stark apparatus. The mixture was cooled and 75 ml. of triethylamine was added, followed by 108 g. of dichloroacetyl chloride added dropwise with stirring and cooling in a room temperature water bath. The solution was allowed to stand after addition was complete, washed with water, dried over anhydrous magnesium sulfate, and the solvent stripped under vacuum. The thick oil wt. 170 g. crystallized on standing and was triturated with dry ether to give 132 g. of the title compound, a white solid, m.p. 99.5-100.5° C.

EXAMPLE IV Preparation of 2-α -naphthyl-3-chloroacetyl oxazolidine.

Nineteen and nine tenths ml. of a benzene solution containing 5 g. of 2-α -naphthyl oxazolidine was combined with 50 ml. of benzene and 2.8 g. of chloroacetyl chloride. To this was added 2.6 g. of triethylamine, dropwise with stirring in an ice bath. The mixture was stirred at room temperature for 30 minutes after addition was complete, washed with water, separated and dried over magnesium sulfate. The solvent was stripped under vacuum. There was obtained a yield of 6.7 g. of an oil, the title compound, N_(D) ³⁰ = 1.6030.

EXAMPLE V Preparation of 2-phenyl-3-chloroacetyl-4,4-dimethyl oxazolidine.

Twenty-one and three tenths ml. of a benzene solution containing 5.3 g. of 2-phenyl-4,4-dimethyl oxazolidine was mixed with 50 ml. of benzene and 3.4 g. of chloroacetyl chloride. To this solution was added 3.1 g. of triethylamine, dropwise with stirring in an ice bath. The mixture was stirred for about 30 minutes after addition was complete and then washed with water, separated and dried over magnesium sulfate and the solvent stripped. There was obtained a yield of 6.5 g. of an oil, the title compound, N_(D) ³⁰ = 1.5364.

EXAMPLE VI Preparation of 2-phenyl-3-dichloroacetyl thiazolidine.

Five grams of 2-phenyl thiazolidine was dissolved in 50 ml. of acetone, 3.1 g. of triethylamine was added and the mixture stirred in a room temperature water bath, while 4.4 g. of dichloroacetyl chloride was added dropwise. The mixture was allowed to stand for about 30 minutes and then poured into water, extracted with methylene chloride, separated, dried over magnesium sulfate, and the solvent stripped under vacuum. There was obtained a yield of 7.3 g. of an oil, the title compound, N_(D) ³⁰ 32 1.5836.

EXAMPLE VII Preparation of 2-m-chlorophenyl-3-dichloroacetyl thiazolidine.

Five grams of 2-m-chlorophenyl thiazolidine was dissolved in 50 ml. of benzene and 2.6 g. of triethylamine and the mixture was stirred in a room temperature water bath, while 3.7 g. of dichloroacetyl chloride was added dropwise. After standing for about 30 minutes, the mixture was washed with water, separated and dried over magnesium sulfate and the benzene stripped under vacuum. There was obtained a yield of 7.2 g. of an oil, the title compound, N_(D) ³⁰ = 1.5805.

EXAMPLE VIII Preparation of 2-(2',6'-dichlorophenyl)3-chloroacetyl thiazolidine.

Twenty-three and five tenths ml. of a benzene solution containing 5.9 g. of 2(2',6'-dichlorophenyl) thiazolidine was combined with 25 ml. of benzene and 2.8 g. of chloroacetyl chloride and the mixture stirred in an ice bath, while 2.6 g. of triethylamine was added dropwise. After standing for about 30 minutes the mixture was washed with water, separated, dried over magnesium sulfate and the benzene stripped off under vacuum. There was obtained a yield of 8 g. of an oil, the title compound, N_(D) ³⁰ = 1.6041.

EXAMPLE IX Preparation of 3-(3-bromopropionyl)5-phenyl oxazolidine.

Four and five tenths grams of 5-phenyl oxazolidine contained in 44.7 g. of benzene solution was mixed with 3.1 g. of triethylamine and stirred in a room temperature water bath, while 5.2 g. of 3-bromopropionyl chloride was added dropwise. After standing for about 30 minutes, the solution was washed with water, separated, dried over magnesium sulfate and the solvent stripped under vacuum. There was obtained a yield of 6 g. of an oil, the title compound, N_(D) ³⁰ = 1.5591.

EXAMPLE X Preparation of 2,2,4-trimethyl-3-dichloroacetyl-5-phenyl oxazolidine.

Twenty-three ml. of a benzene solution containing 5.7 g. of 2,2,4-trimethyl-5-phenyl oxazolidine was mixed with 25 ml. of benzene and 3.1 g. of triethylamine and stripped at room temperature, while 4.4 g. of dichloroacetyl chloride was added dropwise. After standing for about 30 minutes, the mixture was washed with water, separated, dried over magnesium sulfate and stripped under vacuum. The product which crystallized was extracted with ether and precipitated with pentane. There was obtained 3.9 g. of a solid, the title compound, m.p. 126° C.

EXAMPLE XI Preparation of 2-p-chlorophenyl-3-dichloroacetyl oxazolidine.

Twenty-two ml. of a benzene solution containing 5.5 g. of 2-p-chlorophenyl oxazolidine was mixed with 25 ml. of benzene and 3.1 g. of triethylamine and stirred at room temperature, while 4.4 g. of dichloroacetyl chloride was added dropwise. The mixture was allowed to stand for about 30 minutes, washed with water, separated, dried over magnesium sulfate and then stripped. There was obtained a yield of 8.4 g. of an oil, the title compound, N_(D) ³⁰ = 1.5668.

EXAMPLE XII Preparation of 2,5-diphenyl-3(2,3-dibromopropionyl) oxazolidine.

Four and five tenths grams of 2,5-diphenyl oxazolidine was dissolved in 50 ml. of methylene chloride and 5 g. of 2,3-dibromopropionyl chloride was added and the mixture stirred in an ice bath, while 2.1 g. of triethylamine was added dropwise. After standing for about 30 minutes, the mixture was washed with water, separated and dried over magnesium sulfate and stripped under vacuum. There was obtained a yield of 7.1 g. of an oil, the title compound, N_(D) ³⁰ = 1.5734.

The following is a table of the compounds which are prepared according to the aforementioned procedures. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

                                      TABLE I                                      __________________________________________________________________________      ##STR4##                                                                      COMPOUND                                        M.P. or                        NUMBER   R       R.sub.1 R.sub.2                                                                           R.sub.3 R.sub.4                                                                           R.sub.5                                                                           R.sub.6                                                                          X Y N.sub.D.sup.30                 __________________________________________________________________________     1       CHCl.sub.2                                                                             m-NO.sub.2C.sub.6 H.sub. 4                                                              H  H       H  H  H O O 1.5590                         2       CHCl.sub.2                                                                             m-NO.sub.2C.sub.6 H.sub.4                                                               H  CH.sub.3                                                                               CH.sub.3                                                                          H  H O O 1.5448                         3       CH.sub.2 Cl                                                                            m-NO.sub.2C.sub.6 H.sub.4                                                               H  CH.sub.3                                                                               CH.sub. 3                                                                         H  H O O 1.5484                         4       CHCl.sub.2                                                                             C.sub.6 H.sub.5                                                                         H  H       H  H  H O O 1.5490                         5       CCl.sub.3                                                                              C.sub.6 H.sub.5                                                                         H  H       H  H  H O O 1.5398                         6       CHBrCH.sub.3                                                                           C.sub.6 H.sub.5                                                                         H  H       H  H  H O O 1.5490                         7       CCl.sub.2CH.sub.3                                                                      C.sub.6 H.sub.5                                                                         H  H       H  H  H O O 1.5301                         8       CHBr.sub.2                                                                             C.sub.6 H.sub. 5                                                                        H  H       H  H  H O O 1.5808                         9       CHBrCH.sub.2 Br                                                                        C.sub.6 H.sub.5                                                                         H  H       H  H  H O O 1.5712                         10      CClCCl.sub.2                                                                           C.sub.6 H.sub.5                                                                         H  H       H  H  H O O 1.5615                         11      CHCl.sub.2                                                                             m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5550                         12      CCl.sub.3                                                                              m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5475                         13      CH.sub.2 Cl                                                                            m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5590                         14      CH.sub.2 Br                                                                            m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5720                         15      CHBrCH.sub.3                                                                           m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5590                         16      CHBr.sub.2                                                                             m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5833                         17      CHBrCH.sub.2 Br                                                                        m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5718                         18      CHCl.sub.2                                                                             C.sub.6 H.sub.5                                                                         H  C.sub.2 H.sub.5                                                                        H  H  H O O 1.5353                         19      CCl.sub.3                                                                              C.sub.6 H.sub.5                                                                         H  C.sub.2 H.sub.5                                                                        H  H  H O O 1.5310                         20      CHCl.sub.2                                                                             C.sub.2 H.sub.5                                                                         H  H       H  C.sub.6 H.sub.5                                                                   H O O 1.5600                         21      CCl.sub.3                                                                              C.sub.2 H.sub.5                                                                         H  H       H  C.sub.6 H.sub.5                                                                   H O O 1.5455                         22      CHCl.sub.2                                                                             CH.sub.3 CH.sub.3                                                                          H       H  C.sub.6 H.sub.5                                                                   H O O 1.5438                         23      CH.sub.2 Cl                                                                            CH.sub.3 CH.sub.3                                                                          H       H  C.sub.6 H.sub.5                                                                   H O O 1.5450                         24      CHCl.sub.2                                                                             p-CH.sub.3C.sub.6 H.sub.4                                                               H  H       H  H  H O O 1.5440                         25      CCl.sub.3                                                                              p-CH.sub.3C.sub.6 H.sub.4                                                               H  H       H  H  H O O 1.5430                         26      CHBrCH.sub.2 Br                                                                        p-CH.sub.3C.sub.6 H.sub.4                                                               H  H       H  H  H O O 1.5627                         27      CCl.sub.2 CH.sub.3                                                                     p-CH.sub.3C.sub.6 H.sub.4                                                               H  H       H  H  H O O 1.5370                         28      CH.sub.2 Cl                                                                            p-CH.sub.3C.sub.6 H.sub.4                                                               H  H       H  H  H O O 1.5600                         29      CH.sub.2 Cl                                                                            m-CH.sub.3 OC.sub.6 H.sub.4                                                             H  H       H  H  H O O 1.5570                         30      CHCl.sub.2                                                                             m-CH.sub. 3 OC.sub.6 H.sub.4                                                            H  H       H  H  H O O 1.5557                         31      CCl.sub.3                                                                              m-CH.sub.3 OC.sub.6 H.sub.4                                                             H  H       H  H  H O O 1.5479                         32      CCl.sub.2 CH.sub.3                                                                     m-CH.sub.3 OC.sub.6 H.sub.4                                                             H  H       H  H  H O O 1.5380                         33      CHBrCH.sub.2 Br                                                                        m-CH.sub.3 OC.sub.6 H.sub.4                                                             H  H       H  H  H O O 1.5688                         34      CH.sub.2 Cl                                                                             ##STR5##                                                                               H  H       H  H  H O O 1.6030                         35      CHCl.sub.2                                                                              ##STR6##                                                                               H  H       H  H  H O O 1.5980                         36      CCl.sub.3                                                                               ##STR7##                                                                               H  H       H  H  H O O 1.5132                         37      CCl.sub.2 CH.sub.3                                                                      ##STR8##                                                                               H  H       H  H  H O O 1.5921                         38      CH.sub.2 Cl                                                                            C.sub.6 H.sub.5                                                                         H  H       H  CH.sub.3                                                                          H O O 1.5486                         39      CHCl.sub.2                                                                             C.sub.6 H.sub.5                                                                         H  H       H  CH.sub.3                                                                          H O O 1.5423                         40      CCl.sub.3                                                                              C.sub.6 H.sub.5                                                                         H  H       H  CH.sub.3                                                                          H O O 1.5376                         41      CCl.sub.2 CH.sub.3                                                                     C.sub.6 H.sub.5                                                                         H  H       H  CH.sub.3                                                                          H O O 1.5530                         42      CH.sub.2 Cl                                                                            C.sub.6 H.sub.5                                                                         H  CH.sub.3                                                                               CH.sub.3                                                                          CH.sub.3                                                                          H O O 1.5364                         43      CHCl.sub.2                                                                             C.sub.6 H.sub.5                                                                         H  CH.sub.3                                                                               CH.sub.3                                                                          CH.sub.3                                                                          H O O 1.5343                         44      CCl.sub.3                                                                              C.sub.6 H.sub.5                                                                         H  CH.sub.3                                                                               CH.sub.3                                                                          CH.sub.3                                                                          H O O 1.5310                         45      CCl.sub.2 CH.sub.3                                                                     C.sub.6 H.sub.5                                                                         H  CH.sub.3                                                                               CH.sub.3                                                                          CH.sub.3                                                                          H O O 1.5213                         46      CH.sub.2 Cl                                                                            C.sub.6 H.sub.5                                                                         H  H       H  H  H S O 1.5804                         47      CHCl.sub.2                                                                             C.sub.6 H.sub.5                                                                         H  H       H  H  H S O 1.5836                         48      CCl.sub.3                                                                              C.sub.6 H.sub. 5                                                                        H  H       H  H  H S O 1.5950                         49      CCl.sub.2 CH.sub.3                                                                     C.sub.6 H.sub.5                                                                         H  H       H  H  H S O 1.5798                         50      CH.sub.2 CH.sub.2 Br                                                                   C.sub.6 H.sub.5                                                                         H  H       H  H  H S O 1.5983                         51      CHBrCH.sub.2 Br                                                                        C.sub.6 H.sub.5                                                                         H  H       H  H  H S O 110-112                        52      CH.sub.2 Cl                                                                            m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H S O 1.5925                         53      CHCl.sub.2                                                                             m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H S O 1.5805                         54      CCl.sub.3                                                                              m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H S O 1.5940                         55      CCl.sub.2 CH.sub.3                                                                     m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H S O 1.5850                         56      CH.sub.2 CH.sub.2 Br                                                                   m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H S O 1.5931                         57      CHBrCH.sub.2 Br                                                                        m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H S O 1.6038                         58      CH.sub.2 CH.sub.2 Cl                                                                   m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H S O 1.5920                         59      CH.sub.2 Cl                                                                            3,5-Cl.sub.2C.sub.6 H.sub.3                                                             H  H       H  H  H O O 1.5748                         60      CHCl.sub.2                                                                             3,5-Cl.sub.2C.sub.6 H.sub.3                                                             H  H       H  H  H O O 1.5663                         61      CCl.sub.3                                                                              3,5-Cl.sub.2C.sub.6 H.sub.3                                                             H  H       H  H  H O O 1.5613                         62      CCl.sub.2 CH.sub.3                                                                     3,5-Cl.sub.2C.sub.6 H.sub.3                                                             H  H       H  H  H O O 1.5530                         63      CH.sub.2 Cl                                                                            3,5-Cl.sub. 2C.sub.6 H.sub.3                                                            H  H       H  H  H S O 1.6041                         64      CHCl.sub.2                                                                             3,5-Cl.sub.2C.sub.6 H.sub.3                                                             H  H       H  H  H S O 1.6038                         65      CCl.sub.3                                                                              3,5-Cl.sub.2C.sub.6 H.sub.3                                                             H  H       H  H  H S O 1.5962                         66      CCl.sub.2 CH.sub.3                                                                     3,5-Cl.sub.2C.sub.6 H.sub.3                                                             H  H       H  H  H S O 1.5908                         67      CH.sub.2 Cl                                                                            H        H  H       H  C.sub.6 H.sub.5                                                                   H O O 1.5640                         68      CHCl.sub.2                                                                             H        H  H       H  C.sub.6 H.sub.5                                                                   H O O 1.5593                         69      CCl.sub.3                                                                              H        H  H       H  C.sub.6 H.sub.5                                                                   H O O 1.5558                         70      CHBrCH.sub.2 Br                                                                        H        H  H       H  C.sub.6 H.sub.5                                                                   H O O 1.5738                         71      CCl.sub.2 CH.sub.3                                                                     H        H  H       H  C.sub.6 H.sub.5                                                                   H O O 1.5433                         72      CH.sub.2CH.sub.2 Br                                                                    H        H  H       H  C.sub.6 H.sub.5                                                                   H O O 1.5591                         73      CHCl.sub.2                                                                             m-OHC.sub.6 H.sub.4                                                                     H  H       H  H  H O O Waxy Solid                     74      CCl.sub.2 CH.sub.3                                                                     m-OHC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5453                         75      CHCl.sub.2                                                                             p-NO.sub.2C.sub.6 H.sub.4                                                               H  H       H  H  H S O 1.6008                         76      CHCl.sub.2                                                                             C.sub.6 H.sub.5                                                                         H  C.sub.2 H.sub.5                                                                        H  H  H S O 1.5352                         77      CHCl.sub.2                                                                             C.sub.6 H.sub.5                                                                         H  CH.sub.3                                                                               CH.sub.3                                                                          H  H S O 1.5366                         78      CH.sub.2 Cl                                                                            CH.sub.3 CH.sub.3                                                                          CH.sub.3                                                                               H  C.sub.6 H.sub.5                                                                   H O O 1.5021                         79      CHCl.sub.2                                                                             CH.sub.3 CH.sub.3                                                                          CH.sub.3                                                                               H  C.sub.6 H.sub.5                                                                   H O O 126° C.                 80      CCl.sub.3                                                                              CH.sub.3 CH.sub.3                                                                          CH.sub.3                                                                               H  C.sub.6 H.sub.5                                                                   H O O 1.5080                         81      CH.sub.2 BrCH.sub.2                                                                    CH.sub.3 CH.sub.3                                                                          CH.sub.3                                                                               H  C.sub.6 H.sub.5                                                                   H O O 1.5051                         82      CH.sub.2 BrCHBr                                                                        CH.sub.3 CH.sub.3                                                                          CH.sub.3                                                                               H  C.sub.6 H.sub.5                                                                   H O O 1.5450                         83      CH.sub.2 Cl                                                                            o-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5578                         84      CHCl.sub.2                                                                             o-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5595                         85      CH.sub.2 BrCHBr                                                                        o-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5794                         86      CH.sub.2 Cl                                                                            p-ClC.sub. 6 H.sub.4                                                                    H  H       H  H  H O O 1.5688                         87      CHCl.sub.2                                                                             P-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5668                         88      CH.sub.2 BrCHBr                                                                        p-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5814                         89      CCl.sub.2CCl                                                                           p-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H O O 1.5754                         90      CCl.sub.2CCl                                                                           m-ClC.sub.6 H.sub.4                                                                     H  H       H  H  H S O 1.6008                         91      CHCl.sub.2                                                                             C.sub.6 H.sub.5                                                                         H  H       H  C.sub.6 H.sub.5                                                                   H S O 1.5653                         92      CH.sub.2 BrCHBr                                                                        C.sub.6 H.sub.5                                                                         H  H       H  C.sub.6 H.sub.5                                                                   H S O 1.5734                         93      CH.sub.2 Cl                                                                            C.sub.6 H.sub.5                                                                         H  H       H  C.sub.6 H.sub.5                                                                   H S O 1.5723                         94      CHCl.sub.2                                                                             3,4-di-ClC.sub.6 H.sub.4                                                                H  H       H  H  H S O 1.5600                         95      Cl.sub.2 CH                                                                            p-φ-OCH.sub.3                                                                       H  H       H  H  H S O 1.5740                         96      Cl.sub.2 CH                                                                            o-Cl-φ                                                                              H  H       H  H  H S O 97-102° C.              97      Cl.sub.2 CH                                                                            m-F-φ                                                                               H  H       H  H  H S O 1.5650                         98      Cl.sub.2 CH                                                                            CH.sub.3 CH.sub. 3                                                                         CH.sub.2 OH                                                                            H  φ                                                                             H O O 1.5190                         99      Cl.sub.2 CH                                                                            CH.sub.3 CH.sub.3                                                                           ##STR9##                                                                              H  φ                                                                             H O O 1.5070                         100     Cl.sub.2 CH                                                                            CH.sub.3 CH.sub.3                                                                           ##STR10##                                                                             H  φ                                                                             H O O 1.5180                         101     CH.sub.2 Cl                                                                            CH.sub.3 CH.sub.3                                                                          CH.sub.2 OH                                                                            H  φ                                                                             H O O 1.5182                         102     CHCl.sub.2                                                                             m-Clφ                                                                               H  CH.sub.3                                                                               H  CH.sub.3                                                                          H O O 1.5243                         103     CH.sub.2 BrCHBr                                                                        m-Clφ                                                                               H  CH.sub.3                                                                               H  CH.sub.3                                                                          H O O 1.5406                         __________________________________________________________________________

Other examples of compounds falling within the generic formula presented herein, which are preparable by the aforedescribed procedures and which may be formulated into herbicidal compositions and applied as herein illustrated, are:

    ______________________________________                                         R        R.sub.1    R.sub.2                                                                               R.sub.3                                                                            R.sub.4                                                                             R.sub.5                                                                             R.sub.6                                                                            X   Y                             ______________________________________                                         CH.sub.2 Cl                                                                             C.sub.6 H.sub.5                                                                           H      H   H    H    H   O   S                             CHCl.sub.2                                                                              C.sub.6 H.sub.5                                                                           H      H   H    H    H   O   S                             CCl.sub.3                                                                               C.sub.6 H.sub.5                                                                           H      H   H    H    H   O   S                             CH.sub.2 Cl                                                                             C.sub.6 H.sub.5                                                                           H      H   H    H    H   S   S                             CHCl.sub.2                                                                              C.sub.6 H.sub.5                                                                           H      H   H    H    H   S   S                             CCl.sub.3                                                                               C.sub.6 H.sub.5                                                                           H      H   H    H    H   S   S                             CH.sub.2 Cl                                                                             CH.sub.3   CH.sub.3                                                                              H   H    C.sub.6 H.sub.5                                                                     H   O   S                             CHCl.sub.2                                                                              CH.sub.3   CH.sub.3                                                                              H   H    C.sub.6 H.sub.5                                                                     H   O   S                             CCl.sub.3                                                                               CH.sub.3   CH.sub.3                                                                              H   H    C.sub.6 H.sub.5                                                                     H   O   S                             CH.sub.2 Cl                                                                             CH.sub.3   CH.sub.3                                                                              H   H    C.sub.6 H.sub.5                                                                     H   S   S                             CHCl.sub.2                                                                              CH.sub.3   CH.sub.3                                                                              H   H    C.sub.6 H.sub.5                                                                     H   S   S                             CCl.sub.3                                                                               CH.sub.3   CH.sub.3                                                                              H   H    C.sub.6 H.sub.5                                                                     H   S   S                             CH.sub.2 BrCHBr                                                                         m-Cl--C.sub.6 H.sub.4                                                                     H      H   H    CH.sub.3                                                                            H   O   S                             CH.sub.2 BrCHBr                                                                         C.sub.6 H.sub.5                                                                           H      H   H    CH.sub.3                                                                            H   S   S                             CH.sub.2 BrCHBr                                                                         CH.sub.3   CH.sub.3                                                                              H   H    C.sub.6 H.sub.5                                                                     H   O   S                             CH.sub.2 BrCHBr                                                                         CH.sub.3   CH.sub.3                                                                              H   H    C.sub.6 H.sub.5                                                                     H   S   S                             ______________________________________                                    

The herbicides indicated in the tables and elsewhere are used at rates which produce effective control of undesirable vegetation. The range of rates employed herein produce representative results within the recommended amounts set forth by the supplier. Therefore, the weed control in each instance is commercially acceptable within the desired or recommended amount.

It is clear that the classes of herbicidal agents described and illustrated herein are characterized as effective herbicides exhibiting such activity. The degree of this herbicidal activity varies among specific compounds and among combinations of specific compounds within the classes. Similarly, the degree of activity to some extent varies among the species of plants to which a specific herbicidal compound or combination may be applied. Thus, selection of a specific herbicidal compound or combination to control undesirable plant species readily may be made. Within the present invention are prevention of injury to a desired crop species in the presence of a specific compound or combination may be achieved. The beneficial plant species which can be protected by this method is not intended to be limited by the specific crops employed in the examples.

The herbicidal compounds employed in the utility of this invention are active herbicides of a general type. That is, the members of the classes are herbicidally effective against a wide range of plant species with no discrimination between desirable and undesirable species. The method of controlling vegetation comprises applying an herbicidally effective amount of the herein described herbicidal compounds to the area or plant locus where control is desired. The compositions as set forth in this invention include those wherein the preferred active herbicidal compound is selected from EPTC, S-ethyl diisobutyl thiocarbamate, S-propyl dipropyl thiocarbamate, S-2,3,3-trichloroallyl-diisopropyl thiocarbamate, S-ethyl cyclohexyl ethyl thiocarbamate, 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide, S-ethyl hexahydro-1H-azepine-1-carbothioate, 2-chloro-N-isopropylacetanilide, N,N-diallyl-2-chloroacetamide, S-4-chlorobenzyl diethyl thiocarbamate, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, 2-chloro-4,6-bis(ethylamino)-3-triazine, 2(4-chloro-6-ethylamine-s-triazine-2-yl-amino)-2-methylpropionitrile, 2-chloro-4-cyclopropylamino-6-isopropylamino-s-triazine, 2,4-dichlorophenoxyacetic acid, its esters and salts, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea and combinations thereof.

An herbicide as used herein means a compound which controls or modifies the growth of vegetation or plants. Such controlling or modifying effects include all deviations from natural development; for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like. By "plants", it is meant germinant seeds, emerging seedlings and established vegetation including the roots and above-ground portions.

Evaluation Procedures

Flats to be used for growing the crops and weed species were filled with loamy sand soil. Stock solutions of herbicides and antidotes were prepared as follows:

A. Herbicide - 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide -- LASSO 4E -- 6.25 g. of LASSO 4E was diluted in 1000 ml. of water. 100 ml. of this solution was applied using a linear spray table, such that the equivalent of 2 lb/A of LASSO was applied in 80 gal. of water per acre to each flat.

B. Antidote -- of each candidate 95 mg. was dissolved in 15 ml. of acetone with 1% Tween 20® (polyoxyethylene sorbitan monolaurate) so that 11/2 ml. equals 5 lb/A per flat (based on one-half surface area of a flat).

PES and PPI Tank Mixes

In-furrow application of the antidote employed the above stock solutions (A and B). As a preparatory step, a one pint sample of soil was removed from each flat to be retained and used later to cover the seeds after treatment with the additives. The soil was leveled before planting.

Rows one-quarter inch deep were made lengthweise in each treated flat, preparatory to seeding. After seeding, the flats were sectioned into two equal portions using a wooden barrier and one and one-half ml. of additive stock solution (B) was atomized directly onto the exposed seed and into the furrow in one-half of the flat. The untreated section of the flat served as an herbicide check and also made it possible to observe any lateral movement of the antidote through the soil. The seeds were covered with the one pint sample of untreated soil which had been removed earlier.

The herbicide was applied initially on an individual flat basis by spraying on the soil on a linear spray table the required amount of the herbicide stock solution onto the soil, after seeding and antidote treatment of the furrow.

For tank mixes to be applied as pre-emergence surface application or as pre-plant incorporation, application of the following solutions were used. For 2-chloro-2',6'-diethyl-N-methoxymethyl) acetanilide at 2 lb/A 800 mg. 4E was diluted to 200 ml. with deionized water. To prepare a combined tank mix, 4 ml. of the acetanilide stock solution and 3 ml. of the antidote stock solution (B) were mixed. For the pre-plant incorporation, the same mixed stock solution was injected into the soil during incorporation in a 5 gallon rotary mixer. For pre-emergence surface application, the same stock solution was applied to soil surface after seeding.

The flats were placed on greenhouse benches where temperatures were maintained between 70°-90° F. The soil was watered by sprinkling to assure good plant growth. Injury ratings were taken 2 and 4 weeks after the applications were made. Individual flats treated with the herbicide alone were included to provide a basis for determining the amount of injury reduction provided by the herbicide antidotes.

Some of the candidate antidotes were assayed as antidotes to protect various crops against injury from thiocarbamate herbicides. Selected as representative thiocarbamate herbicides were S-ethyl N,N-dipropylthiocarbamate (EPTC, EPTAM®) and S-propyl N,N-dipropylthiocarbamate (VERNAM®). Stock solutions of herbicides and antidotes were prepared and applied in a variety of ways. Soil incorporation, pre-emergence surface application and in-furrow treatment were employed.

Stock solutions for EPTAM® were prepared as follows:

A. 1/2 lb/A: 670 mg. of EPTC 6E (75.5% a.i.) was diluted with 500 ml. of deionized water so that 2 ml. equals 1/2 lb/A/flat.

B. 5 lb/A: 6700 mg. of EPTC 6E (75.5% a.i.) was diluted with 500 ml. of deionized water so that 2 ml. equals 5 lb/A/flat.

Stock solutions for VERNAM®:

C. 3/4 lb/A: 95 mg. of VERNAM® (75% a.i.) was diluted with 100 ml. of deionized water so that 4 ml. applied pre-plant incorporated is equivalent to 3/4 lb/A per flat.

D. 1 lb/A: 633 mg. of VERNAM® (75% a.i.) was diluted with 500 ml. of deionized water so that 4 ml. applied is equivalent to 1 lb/A per flat.

E. 5 lb/A: 633 mg. of VERNAM® (75% a.i.) was diluted with 100 ml. of deionized water so that 4 ml. is equivalent to 5 lb/A per flat.

The following table includes results as percent protection of various crops according to the various procedures discussed above. The percent protection is determined by a comparison with flats not treated with the candidate antidotes of this invention.

                                      TABLE II                                     __________________________________________________________________________                     PPI (5 lb/A)    PES (5 lb/A)                                   COMPOUND                                                                               5 lb/A - IF                                                                            (Tank Mix)      (Tank Mix)                                     NUMBER  Milo                                                                               SC  Milo                                                                               Ft  CG  WG  Milo                                                                               Ft  CG  WG                                 __________________________________________________________________________     LASSO 2 lb/A                                                                           100*                                                                               100*                                                                               50  100 100 100 70  100 100 100                                1**     70  0   0   0   0   0   0   0   0   0                                  2       20  0   0   0   0   0   0   0   0   0                                  3       50  0   0   0   0   0   0   0   0   0                                  4       60  50  100 0   0   0   70  0   0   0                                  6       20  0   0   0   0   0   0   0   0   0                                  10      0   0   80  0   0   0   14  0   0   0                                  11      60  0   60  0   0   0   0   0   0   0                                  14      0   0   40  0   0   0   0   0   0   0                                  15      15  0   60  0   0   0   14  0   0   0                                  18      0   0   40  0   0   0   14  0   0   0                                  20      80  90  100 0   20  10  85  0   0   0                                  21      15  0   0   0   0   0   0   0   0   0                                  22      90  90  100 0   0   0   100 0   0   0                                  23      70  70  0   0   0   0   0   0   0   0                                  24      15  0   40  0   0   0   28  0   0   0                                  27      0   0   40  0   0   0   0   0   0   0                                  29      0   0   40  0   0   0   0   0   0   0                                  32      0   0   40  0   0   0   14  0   0   0                                  35      30  0   0   0   0   0   0   0   0   0                                  42      50  0   20  0   0   0   0   0   0   0                                  43      60  0   0   0   0   0   0   0   0   0                                  46      25  0   40  0   0   0   14  0   0   0                                  47      50  0   0   0   0   0   0   0   0   0                                  48      30  0   0   0   0   0   0   0   0   0                                  49      40  0   0   0   0   0   0   0   0   0                                  50      50  0   40  0   0   0   0   0   0   0                                  51      30  0   0   0   0   0   0   0   0   0                                  52      0   0   40  0   0   0   28  0   0   0                                  53      50  0   0   0   0   0   0   0   0   0                                  54      20  0   0   0   0   0   0   0   0   O                                  55      60  0   20  0   0   0   28  0   0   0                                  56      20  0   20  0   0   0   0   0   0   0                                  57      30  0   0   0   0   0   0   0   0   0                                  58      60  0   0   0   0   0   0   0   0   0                                  59      30  0   80  0   30  0   0   0   0                                      63      20  0   80  0   0   0   14  0   0   0                                  64      50  0   0   0   0   0   0   0   0   0                                  65      30  0   0   0   0   0   0   0   0   0                                  67      0   0   40  0   0   0   28  0   0   0                                  68      80  0   0   0   0   0   0   0   0   0                                  70      40  0   0   0   0   0   0   0   0   0                                  72      50  0   0   0   0   0   0   0   0   0                                  73      15  0   60  0   0   0   0   0   0   0                                  75      40  0   80  0   0   0   65  0   0   0                                  76      40  0   0   0   0   0   0   0   0   0                                  77      40  0   0   0   0   0   0   0   0   0                                  78      5   --  16  0   0   0   20  0   0   0                                  79      80  --  50  0   0   0   50  0   0   0                                  80      20  --  0   0   0   0   16  0   0   0                                  81      15  --  0   0   0   0   0   0   0   0                                  83      15  --  0   0   0   0   16  0   0   0                                  84      60  --  50  0   0   0   50  0   0   0                                  85      0   --  20  0   0   0   50  0   0   0                                  87      50  --  40  0   0   0   67  0   0   0                                  88      0   --  30  0   0   0   16  0   0   0                                  89      30  --  30  0   0   0   16  0   0   0                                  90      30  --  0   0   0   0   0   0   0   0                                  91      15  --  0   0   0   0   16  0   0   0                                  92      40  --  0   0   0   0   0   0   0   0                                  94      40  --  50  0   0   0   40  0   0   0                                  __________________________________________________________________________      Application Method:                                                            In-Furrow - IF                                                                 Pre-Plant Incorporation - PPI (Tank Mix)                                       Pre-Emergence Surface Application - PES (Tank Mix)                             Crop Species: Milo - (Sorghum vulgare)                                         Weed Species:                                                                  Shatter cane - SC (Sorghum bicolor)                                            Foxtail - ft (Sataria viridis)                                                 Crabgrass - CG (Digitaria sanguinalis)                                         Watergrass - WG (Echinochloa crusgalli)                                        *% injury                                                                      **% protection                                                                 -- not tested.                                                           

Thiocarbamate Herbicide Multicrop Screen

Treated flats were seeded with DeKalb XL-44 corn (Zea maize), sugarbeets (Beta vulgare), small seeded gray striped sunflower (Helianthus annus), soybeans (Glycine max) and oilseed rape (Brassica napus), milo [sorghum] (sorgum vulgare), wheat (Triticum aestivum), green foxtail (Sataria viridis), rice (Oryza sativa) and barley (Hordeum vulgare). Seeds were then covered with the pint soil sample removed prior to seeding.

The flats were then placed on greenhouse benches where temperatures were maintained between 70°-90° F. The soil was watered by sprinkling to assure good plant growth.

Injury ratings were taken 2 and 4 weeks after the treatments were applied. Soil treated with the herbicide alone at the indicated rate was included to provide a basis for determining the amount of injury reduction provided by the herbicide antidotes. The percent protection of various representative crops is reported in Table III. The percent protection is determined by a comparison with flats not treated with the candidate antidote.

                                      TABLE III                                    __________________________________________________________________________     MULTICROP SCREEN RESULTS                                                               Method of                                                              COMPOUND                                                                               Antidote                                                                              Herbicide                                                                              Crop   Per Cent                                         NUMBER  Application                                                                           Rate lb/A                                                                              Protected                                                                             Protection                                       __________________________________________________________________________     1       PPI    EPTC/1/2                                                                               Milo   30                                                                      Rice   63                                                                      Barley 30                                               2       PPI    EPTC/5  Corn   100 (2 wks)                                      3       PPI    EPTC/5  Rice   63                                                                      Corn   100                                              4       PPI    EPTC/1/2                                                                               Milo   50                                               6       PPI    EPTC/1/2                                                                               Milo   40                                               9       PPI    EPTC/1/2                                                                               Rice   100                                                                     Barley 50                                               11      PPI    EPTC/1/2                                                                               Milo   50                                                                      Corn   100                                              13      PPI    EPTC/5  Sunflower                                                                             67                                               15      PPI    EPTC/1/2                                                                               Rice   100                                                             EPTC/5  Corn   65                                               16      PPI    EPTC/1/2                                                                               Rice   100                                                             EPTC/5  Corn   65                                               17      PPI    EPTC/1/2                                                                               Rice   100                                              22      PPI    EPTC/1/2                                                                               Milo   90                                                              EPTC/5  Corn   100                                              23      PPI    EPTC/1/2                                                                               Milo   67                                                              EPTC/1/2                                                                               Rice   55                                                              EPTC/5  Sunflower                                                                             30                                               28      PPI    EPTC/5  Sunflower                                                                             67                                               31      PPI    EPTC/5  Sugarbeet                                                                             70                                               33      PPI    EPTC/1/2                                                                               Rice   44                                                              EPTC/1/2                                                                               Barley 40                                               34      PPI    EPTC/1/2                                                                               Milo   10                                               35      PPI    EPTC/1/2                                                                               Milo   45                                               36      PPI    EPTC/5  Sugarbeet                                                                             80                                               38      PPI    EPTC/5  Corn   33                                               39      PPI    EPTC/1/2                                                                               Barley 40                                                              EPTC/5  Corn   55                                               40      PPI    EPTC/5  Corn   22                                               41      PPI    EPTC/5  Sunflower                                                                             67                                               42      PPI    EPTC/5  Corn   22                                               47      PPI    EPTC/1/2                                                                               Milo   75                                                                      Wheat  67                                                                      Rice   78                                                                      Barley 63                                                              EPTC/5  Corn   100                                              48      PPI    EPTC/1/2                                                                               Milo   25                                               51      PPI    EPTC/1/2                                                                               Barley 67                                               53      PPI    EPTC/1/2                                                                               Barley 50                                                              EPTC/5  Corn   100                                              54      PPI    EPTC/5  Corn   40                                               57      PPI    EPTC/5  Oilseed rape                                                                          67                                               60      PPI    EPTC/5  Corn   100                                              65      PPI    EPTC/5  Corn   50                                               67      PPI    EPTC/1/2                                                                               Rice   100                                              68      PPI    EPTC/1/2                                                                               Rice   100                                              70      PPI    EPTC/1/2                                                                               Wheat  78                                                                      Barley 85                                                                      Rice   100                                              72      PPI    EPTC/1/2                                                                               Rice   85                                                              EPTC/1/2                                                                               Barley 85                                               73      PPI    EPTC/1/2                                                                               Barley 50                                               75      PPI    EPTC/1/2                                                                               Rice   85                                                                      Barley 72                                                              EPTC/5  Corn   50                                               76      IF/5 lb/A                                                                             EPTC/5  Corn   100                                              77      IF/5 lb/A                                                                             EPTC/5  Corn   50                                               VERNAM 6E      VERNAM/5                                                                               Corn   60* Injury                                                              Milo   100                                                                     Wheat  98                                                                      Barley 90                                               2       IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   50                                               3       IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   50                                               4       IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   100                                              11      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   100                                                             VERNAM/3/4                                                                             Milo   50                                               18      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   100                                              20      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   100                                                             VERNAM/3/4                                                                             Milo   60                                               22      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   100                                                             VERNAM/3/4                                                                             Milo   90                                               23      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   100                                              24      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   84                                                              VERNAM/3/4                                                                             Milo   40                                               26      IF/5 lb/A                                                                             VERNAM/3/4                                                                             Barley 67                                               35      IF/5 lb/A                                                                             VERNAM/3/4                                                                             Corn   67                                                              VERNAM/3/4                                                                             Milo   40                                               38      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   50                                               39      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   100                                                             VERNAM/3/4                                                                             Barley 55                                               40      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   67                                               47      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   100                                                             VERNAM/3/4                                                                             Milo   50                                               53      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   100                                              60      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   100                                              78      IF/5 lb/A                                                                             VERNAM/1                                                                               Milo   50                                                              VERNAM/5                                                                               Corn   22                                               79      IF/5 lb/A                                                                             VERNAM/1                                                                               Milo   60                                                              VERNAM/5                                                                               Corn   88                                               80      IF/5 lb/A                                                                             VERNAM/1                                                                               Milo   30                                                              VERNAM/5                                                                               Corn   88                                               81      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   20                                               82      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   45  (2 wks)                                      83      IF/5 lb/A                                                                             VERNAM/1                                                                               Barley 50                                               84      IF/5 lb/A                                                                             VERNAM/1                                                                               Milo   40                                                              VERNAM/5                                                                               Corn   88                                               85      IF/5 lb/A                                                                             VERNAM/1                                                                               Wheat  40                                                              VERNAM/1                                                                               Barley 45                                                              VERNAM/5                                                                               Corn   67                                               86      IF/5 lb/A                                                                             VERNAM/1                                                                               Barley 55                                                              VERNAM/5                                                                               Corn   78                                               87      IF/5 lb/A                                                                             VERNAM/1                                                                               Milo   50                                                              VERNAM/1                                                                               Barley 45                                                              VERNAM/5                                                                               Corn   67                                               88      IF/5 lb/A                                                                             VERNAM/1                                                                               Barley 55                                               90      IF/5 lb/A                                                                             VERNAM/1                                                                               Barley 33                                                              VERNAM/5                                                                               Soybeans                                                                              30                                               91      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   36                                               94      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   23                                               95      IF/5 lb/A                                                                             VERNAM/1                                                                               Wheat  44                                                              VERNAM/1                                                                               Barley 44                                                              VERNAM/5                                                                               Corn   100                                              96      IF/5 lb/A                                                                             VERNAM/1                                                                               Wheat  67                                                              VERNAM/1                                                                               Barley 44                                                              VERNAM/5                                                                               Corn   37.5                                             97      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   87.5                                             98      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   37.5                                             99      IF/5 lb/A                                                                             VERNAM/5                                                                               Corn   75                                               100     IF/5 lb/A                                                                             VERNAM/1                                                                               Milo   20                                                              VERNAM/1                                                                               Barley 22                                               101     IF/5 lb/A                                                                             VERNAM/1                                                                               Milo   20                                                              VERNAM/1                                                                               Barley 44                                               102     IF/5 lb/A                                                                             VERNAM/6**                                                                             Corn   100                                              103     IF/5 lb/A                                                                             VERNAM/1                                                                               Wheat  33                                                              VERNAM/1                                                                               Barley 33                                               __________________________________________________________________________      **Stock solution for VERNAM 6E at 6 lb/A PPI (pre-plant incorporated) 380      mg/500 ml. water; such that 4 ml. = 6 lb/A PPI                           

The compounds and compositions of this invention were employed in effective herbicidal compositions comprising the antidote and a representative thiocarbamate herbicide and the antidote and a representative halogenated acetanilide herbicide, as described hereinabove. The herbicidal compositions were tested in the following manner.

The compositions of the present invention for the protection of cultivated crop plants comprise an active herbicidal compound and an antidote therefore selected from the abovedescribed compounds. The compositions of herbicide and antidote can be prepared by conventional methods through the thorough mixing and grinding of the active herbicide agents and the antidote with suitable carriers and/or other distribution media, possibly with the addition of dispersion agents or solvents.

The antidote compounds and compositions of the present invention can be used in any convenient form. Thus, the antidote compounds can be formulated into emulsifiable liquids, emulsifiable concentrates, liquid, wettable powder, powders, granular or any other convenient form. In its preferred form, a non-phytotoxic quantity of an herbicidal antidote compound is admixed with a selected herbicide and incorporated into the soil prior to or after planting the seed. It is to be understood, however, that the herbicides can be incorporated into the soil and thereafter the antidote compound can be incorporated into the soil. Moreover, the crop seed itself can be treated with a non-phytotoxic quantity of the compound and planted into the soil which has been treated with herbicides, or untreated with the herbicide and subsequently treated with the herbicide. The addition of the antidote compound does not affect the herbicidal activity of the herbicides.

The amount of antidote compound present can range between about 0.0001 to about 30 parts by weight of antidote compound described herein per each part by weight of herbicide. The exact amount of antidote compound will usually be determined on economic ratios for the most effective amount usable. It is understood that a non-phytotoxic quantity of antidote compound will be employed in the herbicidal compositions described herein. 

What is claimed is:
 1. A compound according to the formula ##STR11## in which R is haloalkyl containing from 1 to 6 carbon atoms, inclusive, and the term halo includes chloro and bromo as mono, di, tri and tetra substitutions and chloroalkenyl containing 2 to 4 carbon atoms and the chloro substituents are present as mono, di, tri or tetra substitutions; in which X and Y are independently oxygen or sulfur; R₁ is hydrogen, lower alkyl or phenyl; R₂ is hydrogen or lower alkyl; R₃ is hydrogen or lower alkyl; R₄ is hydrogen or lower alkyl; R₅ is phenyl and R₆ is hydrogen.
 2. A compound according to claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R₁ is hydrogen, R₂ is hydrogen, R₃ is hydrogen and R₄ is hydrogen.
 3. A compound according to claim 2 in which R is chloroalkyl.
 4. A compound according to claim 2 in which R is dichloromethyl.
 5. A compound according to claim 2 in which R is trichloromethyl.
 6. A compound according to claim 2 in which R is 1,2-dibromoethyl.
 7. A compound according to claim 2 in which R is 1,1-dichloroethyl.
 8. A compound according to claim 2 in which R is 2-bromoethyl.
 9. A compound according to claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R₁ is lower alkyl, R₂, R₃ and R₄ are each hydrogen.
 10. A compound according to claim 9 in which R is dichloromethyl and R₁ is ethyl.
 11. A compound according to claim 9 in which R is trichloromethyl and R₁ is ethyl.
 12. A compound according to claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₃ and R₄ are each hydrogen.
 13. A compound according to claim 12 in which R is dichloromethyl, R₁ is methyl and R₂ is methyl.
 14. A compound according to claim 12 in which R is monochloromethyl, R₁ is methyl and R₂ is methyl.
 15. A compound according to claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₃ is lower alkyl and R₄ is hydrogen.
 16. A compound according to claim 15 in which R is monochloromethyl and R₁, R₂ and R₃ are each methyl.
 17. A compound according to claim 15 in which R is dichloromethyl and R₁, R₂ and R₃ are each methyl.
 18. A compound according to claim 15 in which R is trichloromethyl and R₁, R₂ and R₃ are each methyl.
 19. A compound according to claim 15 in which R is 2-bromoethyl and R₁, R₂ and R₃ are each methyl.
 20. A compound according to claim 15 in which R is 1,2-dibromoethyl and R₁, R₂ and R₃ are each methyl.
 21. A compound according to claim 1 in which X is sulfur, Y is oxgyen, R is haloalkyl, R₁ is phenyl, R₂, R₃ and R₄ are each hydrogen.
 22. A compound according to claim 21 in which R is dichloromethyl.
 23. A compound according to claim 21 in which R is 1,2-dibromoethyl.
 24. A compound according to claim 21 in which R is mono-chloroethyl.
 25. A compound according to claim 1 in which X is oxygen, Y is sulfur, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₃ and R₄ are each hydrogen.
 26. A compound according to claim 1 in which X is sulfur, Y is sulfur, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₃ and R₄ are each hydrogen.
 27. A compound according to claim 1 in which X is oxygen, Y is sulfur, R is haloalkyl, R₁ is hydrogen, R₂ is hydrogen, R₃ is hydrogen and R₄ is hydrogen.
 28. A compound according to claim 1 in which X is sulfur, Y is sulfur, R is haloalkyl, R₁ is hydrogen, R₂ is hydrogen, R₃ is hydrogen and R₄ is hydrogen.
 29. A compound according to claim 1 in which X is oxygen, Y is sulfur, R is haloalkyl, R₁ is lower alkyl, R₂, R₃ and R₄ are each hydrogen.
 30. A compound according to claim 1 in which X is sulfur, Y is sulfur, R is haloalkyl, R₁ is lower alkyl, R₂, R₃ and R₄ are each hydrogen.
 31. A compound according to claim 1 in whixh X is oxygen, Y is sulfur, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₃ is lower alkyl and R₄ is hydrogen.
 32. A compound according to claim 1 in which X is sulfur, Y is sulfur, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₃ is lower alkyl and R₄ is hydrogen. 